Effect of Surface Stoichiometry on Blinking and Hole Trapping Dynamics in CdSe Nanocrystals

Busby, Erik; Anderson, Nicholas C.; Owen, Jonathan S.; Sfeir, Matthew Y.

doi:10.1021/acs.jpcc.5b08243

Effect of Surface Stoichiometry on Blinking and Hole Trapping Dynamics in CdSe Nanocrystals

Journal Article · Fri Nov 13 00:00:00 EST 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b08243· OSTI ID:1370370

Busby, Erik ^[1]; Anderson, Nicholas C. ^[2]; Owen, Jonathan S. ^[2]; Sfeir, Matthew Y. ^[3]

Brookhaven National Lab. (BNL), Upton, NY (United States); Columbia Univ., New York, NY (United States)
Columbia Univ., New York, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Here, we measure the photoinduced carrier dynamics as the surface composition of CdSe nanocrystals is systematically varied from metal rich (~80% surface Cd) to nearly stoichiometric (~50% surface Cd). Using time-resolved optical spectroscopy, we determine that the luminescence lifetime is controlled by the rate of hole trapping at the newly exposed surface selenium atoms. However, the increased rate of the photoluminescence decay is not sufficient to explain the decreased photoluminescence quantum yield, and requires a growing proportion of nanocrystals in a dark or “OFF” state to explain the data. A global kinetic model is proposed that relates the fraction of selenium sites to the rate of hole trapping. A linear relationship between the rate of hole trapping and the fraction of exposed Se sites (x_Se) is observed within the range of accessible stoichiometries (x_Se = 0.5–0.2). Extrapolation to higher surface cadmium fractions suggests that not all Se sites serve as effective hole traps. These findings confirm the strong nonlinear dependence of the fluorescence yield on the nanocrystal stoichiometry.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Re-Defining Photovoltaic Efficiency Through Molecule Scale Control (RPEMSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001085; SC0006410; SC0012704

OSTI ID:: 1370370

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 49 Vol. 119; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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